Compounds having an affinity for cotton



Patented May 24, 1932 UNITED STATES PATENT OFFICE WERNER LANGE, OF DESS AU-ZIEBIGK IN ANHALT, GERMANY, ASSIGNOR TO GENERAL ANILINE WORKS, IN (3., OF NEW YORK, N. Y., A CORPORATION OF DELAWARE COMPOUNDS HAVING AN AFFINITY FOR COTTON No Drawing. Application filed July 8, 1930, Serial No. 466,592, and in Germany July 24, 1929.

wherein R represents the residue of an aromatic carboxylic acid, or a plurality of such aromatic radicles linked one to another by an atomic linkage of the group consisting of and A represents an atomic linkage of the group consisting of N=N,--N--N- I have found that these new compounds bearing a terminal amino group, are obtainableby a cautious reduction of a carboxylic acid of an aromatic diamino compound in which both amino groups are nitro-benzoylated or in which only one amino group is substituted by a nitrobenzoyl radicle. Finally, I may start from a mononitrobenzoylated i aromatic amino nitro compound and I obtain an analogous manner carboxylic acid compounds of the general formula mentioned above. Generally, the new compounds are feebly colored; they dye cotton directly, can be diazotized and coupled with azo components to form dyes on the fiber.

The following examples illustrate the invention, the parts being by weight Example 1.l7.2 parts of sodium 1.4:-di- 4-nitrobenzoylamino) -benzene 2 carboxylate, obtainable by causing lAt-diaminoben zene-Q-carboxylic acid to react with I-nitrobcnzoylchloride, are suspended in water and there is added an excess of sodium hydroxide and 23.5 parts of anhydrous sodium sulfide and the mixture is stirred for some hours at the ordinary temperature. The product of the reaction is pressed and purified by reprecipitation from water.

The product obtained forms in the dry state an orange colored powder, soluble in hot water, to a green-yellow solution. The green-yellow color of the solution poured on blotting paper is not altered when treated with acetic acid, it becomes light yellow by a mineral acid and more reddish by sodium hydroxide. When cooling the solution, the compound is partly separated in form of flakes. Hydrochloric acid precipitates the compound in form of a yellow, gelatinous mass. .It dissolves in concentrated sulfuric acid with green-yellow color.

Probably it corresponds to the formula:

COONa I00 ()0 NH IIIH GOONa NaOOO r r O 0 (I NE: NH;

wherein X means 0, 1 or a whole number greater than 1 and wherein N=N may be substituted by NN. o

The new compound dyes cotton bright yellow and when diazotized on the fiber and coupled with 1-phenyl-8-methyl-5-pyrazolone to washing and light.

Instead of sodium sulfide other reducing agents may be used, such as zinc dust and acetic acid.

Example 2-323 parts of sodium l-aminoat (4 nitrobenzoylamino) benzene 2 car- When cooling, from the solution flakes are separated; by addition of hydrochloric acid greyish yellow flakes are precipitated. The solution poured on blotting paper shows the reactions indicated in Example 1. The solution in concenerated sulfuric acid is yellow.

Probably the compound in form of its sodium salt corresponds to the formula:

NaOOO O.N NH OO NO.

COOH

obtainable by condensing l-aminobenzene-Q- carboxylic acid with 4-nitrobenzo lchloride and subsequently nitrating (the melting point of the product is 220222 (1; the procluct is nearly insoluble in water and sparingly soluble in alcohol and acetone) are stirred with about 750 parts of water and there are added parts of sodium hydroxide solution of 40 Be. and 24: parts of anhydrous sodium sulfide. Stirring is continued at room temperature for several hours. After addition of common salt, the product is separated from the solution in the usual manner and purified by reprecipitation from water.

A powder of orange color is obtained easily soluble in hot water to a yellow solution. In the cold the solution gelatinizes. Hydrochloric acid forms a yellow colloidal solution. Poured on blotting paper, it shows the chemical reactions indicated in Example 1. The solution in concentrated sulfuric acid is yellow.

Probably the compound corresponds to the formula e o gae NaOOO l ('10 (I10 ITIH IPIH O GOONa COOi a NHz NH:

wherein X means 0, 1 or a whole number greater than 1 and wherein N=N- may be substituted by It dyes cotton light yellow and when diazotized on the fiber and coupled with phenylmethylpyrazolone, it yields a reddish yellow, or if coupled with 2-hydroxynaphthalene a scarlet.

My invention is not limited to the fore- OOONa going examples nor to the specific details given therein.

Thus, for instance, I may use as a starting material a monoor di-nitrobenzoylated diamino carboxylic acid of the naphthalene series or a nitro monobenzoylamino derivative of a naphthalene carboxylic acid, a nitrobenzoylated benzidine dicarboxylic acid, a

As shown in the examples and the foregoing paragraph, a great number of various starting materials are suitable for being subjected to my reduction process in order to be transformed to new products having an excellent afiinity for the chemically unprepared cotton fiber. These starting materials are characterized by the presence of at least one nitrobenzoyl group yielding by a slight reduction the atomic linkage between two or more molecules, and they belong to the ben zene and naphthalene series and include such compounds as contain two benzene nuclei, such as diphenyl and stilbene, and such compounds in which two or more benzene nuclei are linked together by an atomic linkage of the group consisting of HNC'ONH,

and

In the following claims the term a compound of the benzene series is intended to include such possibilities.

What I claim is 1. As new products the compounds which have an afiinity for cotton, are diazotizable on the fiber and are carboxylic acids of compounds of the general formula:

wherein R represents a radicle of a compound corresponding probably to the general formula: Y

OOH OOOH wherein R represents a radicle of a compound of the benzene series or a radicle of the naphthalene series, X and X stand for hydrogen, or bound to the nitrogen by a CO group for a radicle of a compound of the benzene series or a radicle of the naphthalene series, said radicle bearing a terminal NH group, and A represents an atomic linkage of the group consisting of N=N and p 4. As new products the compounds which have an aflinity for cotton, are diazotizable on, the fiber and are salts of carboxylic acids corresponding probably to the general formula:

OOH

of the benzene series or a radicle of the naphthalene series, and A represents an atomic linkage of the group consisting of N=N and 2. As new products the compounds which have an affinity for cotton, are diazotizable on the fiber and are salts of carboxylic acids corresponding probably to the general formula:

COOH

OOOH

wherein R represents a radicle of a compound of the benzene series or a radicle of the naphthalene series, X and X stand for hydrogen, or bound to the nitrogen by a -CO group for a radicle of a compound of the benzene series or a radicle of the naphthalene series, said radicle bearing a terminal YH group, and A represents an atomic linkage of the group consisting of N=N and NN. \O/

3. As new products the compounds which OOH wherein A represents an atomic linkage of the group consising of the azoand the azoXy group, and wherein X and X stand for hydrogen or, bound to the nitrogen by a CO group for a radicle of a compound of the benzene series or a radicle of the naphthalene series, said radicle bearing a terminal NH group.

6. As new products the compounds which have an aifinity for cotton, are diazotizable on the fiber and are salts of carboxylic acids corresponding probably to the general formula:

have an afiinity for cotton, are diazotizable on the fiber and are salts of carboxylic acids COOH OOOHa wherein A represents an atomic linkage of the group consisting of the azoand the azoxy group, and wherein X and X stand for hydrogen or, bound to the nitrogen by a COgroup for a radicle of a compound of the benzene series or a radicle of the naphthalene series, said radicle bearing aterminal NH group. n

1 7. As new products the compounds which have an affinity for cotton, are diazotizable on the fiber and are salts of carboxylic acids corresponding probably to the general formula:

wherein A represents an atomic linkage of the group consisting of the azoand the azoxy group and wherein X stands for hydrogen or bound to the nitrogen by a CO group for a radicle of a compound of the benzene series or a radicle of the naphthalene series, said radicle bearing a terminal NH group.

8. As new products the compounds which have an affinity for cotton, are diazotizable on the fiber and are salts of carboXylic acids corresponding probably to the general formula:

ylic acids corresponding probably to the general formula:

wherein X means 0, 1 or a whole number greater than 1 and wherein -N=N may be substituted by 11. The process of producing new com- I l COOH wherein A represents an atomic linkage of the group consisting of the azoand the azoxy group, and wherein X and X stand for hydrogen or, bound to the nitrogen by a C() group for a radicle of a compound of the benzene series or a radicle of the naphthalene series, said radicle bearing a terminal H group.

9. As new products the componds which have an afiinity for cotton, are diazotizable on the fiber and are salts of carboXylic acids corresponding probably to the general formula:

COOH

wherein A represents an atomic linkage of the group consisting of the azoand the azoxy group and wherein X stands for a hydrogen or bound to the nitrogen by a CO group for a radicle of a compound of the benzene series or a radicle of the naphthalene series, said radicle bearing a terminal NH group.

10. As new products the compounds which have an afiinity for cotton, are diazotizable on the fiber and are salts of carboX- COOH pounds having an affinity for cotton and being diazotizable on the fiber, which process comprises treating with a reducing agent a compound of the general formula:

wherein R represents a radicle of a compound of the benzene series or a radicle of the naphthalene series and Y stands for a substituent of the group consisting of NO reducing agent being present in an amount necessary for a partial reduction of the nitro groups to form an atomic linkage between two molecules of the nitrobenzoyl compound of the group consisting of azo and azoxy.

12. The process of producing new compounds having an affinity for cotton and being diazotizable on the fiber, which process comprises treatmg' wlth a reducing agent a compound of the general formula:

YOflH NH-C OO6H4N02 v coon wherein Y stands for a substituent of the group consisting of NO NH and NHCOC H NO said reducing agent being present in an amount nec- YQNH-OO-ONO:

wherein Y stands for a substituent of the group consisting of NO -NH and NHCOC H NO said reducing agent being present in an amount necessary for a partial reduction of the nitro groups to form an atomic linkage between two molecules of the nitrobenzoyl compound of the group consisting of azo and azoxy.

14. The process of producing a new com pound having an afiinity for cotton and being diazotizable on the fiber, which comprises treating 1.4-di- (4-nitrobenzoyla1nino) -benzene carboxylic acid with a reducing agent, said reducing agent being present in an amount necessary for a partial reduction of the nitro groups to form an atomic linkage between two molecules of the nitrobenzoyl compound of the group consisting of azo and azoxy.

15. The process which comprises treating about 47.2 parts by weight of 1.4-di- (4'-nitrobenzoylamino) benzene- Q-carboxylic acid in the presence of an excess of a diluted sodium hydroxide solution at room temperature with about 23.5 parts by weight of anhydrous sodium sulfide.

In testimony whereof I afiix my signature.

WERNER LANGE. 

